Production of halogenated ethers



Patented Mar. 30, 1937 UNITED STATES PRODUCTION OF HALOGENATED ETHEBSFritz Straus, Berlin, Germany, assignor to I. G.

Farbenindustrie Aktiengesellschalt, Franklorton-the-Main, Germany NoDrawing. Original Serial No. 14,437. December 18, 1935, S many April 10,1934 8 Claims.

The present invention relates to the production of halogenated ethers.This application has been divided out of my copending application Ser.No. 14,437, filed April 3rd, 1935.

6 I have found that halides of the general formula in which R stands forhydrogen, alkyl, aryl or aralkyl and R for alkyl, aryl or aralkyl and Xfor halogen can be added on to compounds containing at least oneolefinic double bond. It is 15 not necessary to employ the said halidesin, isolated and pure form, but also mixtures of compounds capable ofreacting like such halides, as for example mixtures of aldehydes withalcohols and hydrogen halides may be employed.

The reaction takes place with formation of halogenated ethers. Thus forexample, chlormethyl methyl ether reacts with trimethylethylene withformation of 1-methoxy-2.3-dimethyl- 3-chlorbutane corresponding to theequation:

25 HaC(OCHs)C1-l-CHs.CH:C(CH3)2 CHsOCH2.CH(CH3) .ccucm) 2 chlormethylmethyl ether reacts with butadiene with formation ofl-methoxy--chlor-pentene-3, 30 corresponding to the equation:

Halides suitable for the present process are for 5 example monochlormethyl ether CH2C1(OCH3),

alpha-chlor diethyl ether CH3CHCI(OC2H5), alpha-chlormethvl dodecylether CH2CI(OC12H25) 4o alpha-chlor-didodecyl ether CuHzaCHCKOCmHzs)alpha-chlor-benzyl methyl ether CsHsCHCKOCHa) or its derivativessubstituted in the nucleus, alpha-chlorcinnamic ethyl ether applicationApril 3, 1935,

Divided and this application erlal No. 55,006. In Ger- (Cl. zoo-149)hydrogen chloride, of acetaldehyde with ethanol and hydrogen chloride,of formaldehyde with dodecyl alcohol and hydrogen chloride, and so on.

As compounds having an olefinic double bond suitable for the process maybe mentioned for example cyclohexene, the homologues of ethylene, suchas trimethylethylene, and further substances having conjugated doublebonds as, for example, butadiene and its homologues, such as isoprene,and also 1.2-dihydrobenzene.

The reaction may be efiected, if desired, in the presence of solvents,as for example benzene, and, acetylenetctrachloride.

The speed of the reaction depends on the chemical nature of theunsaturated compound and the chloride employed. The reaction may beaccelerated by adding catalysts, of which anhydrous metal halides, suchas mercury chloride and zinc chloride, may be mentioned.

The reaction products thus obtained are suitable as solvents or may beemployed as interme- Example 1 16 parts of liquefied. butadiene arecaused to react with 52 parts of alpha-chlor-benzyl methyl ether,obtainable as described in Liebigs Annalen A. D. 1932, volume 493, page203, in a pressuretight vessel after adding as catalyst from about 0.3to 0.7 part of mercuric chloride. The mixture is kept at roomtemperature for two days, after which time the reaction is practicallyfinished.

The crude reaction product is shaken with an aqueous solution of sodiumchloride and isolated therefrom by extracting with ether in the usualmanner,

The l-phenyl-1-methoxy-5-chlor-pentene-3 of the formula CaH5CH(OCHs)CH2.CH 2 CH.CH2C1 thus obtained in an excellent yield is a colorless,viscous liquid smelling like acetal and boiling at 93 C. at a pressureof 0.01 mm. (mercury gauge) and having the-specific gravity The partsare by weight if not Example 2 3 to 4 parts of mercuric chloride areadded in a pressure-tight vessel to a mixture oi 27 parts of chlormethylmethyl ether with 10.5 parts of ll'quefled butadiene. When the mixtureis warmed to room temperature. reaction takes place with evolution ofheat, which is taken of! by cooling with water. Thus the temperature iskept at about 30 C. for 24 hours.

The reaction product obtained in a yield of 60 to 70 per cent is1-methoxy-5-chlor-pentene-3 of the formula CH:.O.CH:.CH:CH:CH.CH:C1 itcan be isolated as described in Example 1.

when purified by distillation it is an easily mobile liquid having astrong radish-like odor. It boils at 118 C. at normal pressure and hasthe specific gravity d 1.0022 Examples 36 parts of crudealpha-brom-benzyl methyl ether obtained by reacting with acetylbromideon benzaldehyde-dimethyl acetal and removing the volatile by-productsunder reduced pressure as described in Liebigs Annalen A. D. 1932,volume 498, page 124. are added to 6 parts oi liquefied butadiene, nocatalyst being present. The reaction is finished after the mixture hasbeen kept at room temperature for 3 days. The reaction product isl-phenyl-1-methoxy-5-brompentene-3 of the formula v CeH5.CH. (OCHa).CH.CH CI-LCHsBl it is isolated with a yield of 30 per cent in the manner described in Example 1, it boils at 92 C. at 40 a pressure of 0.05millimeter mercury gauge.

Example 4 Molecular proportions of 1.2-dihydro-benzene andalphachlor-benzyl methyl ether are mixed in the presence of somecentigrams of mer-' curic chloride. The reaction takes place at roomtemperature with evolution of heat, which is'taken off by cooling withwater.

The reaction product is a methoxy-benzylchlor-cyclohexene the structuralformula of which is unknown. It boils at 112 C. at a pressure of 0.05millimeter mercury gauge, the specific gravity being The yield is almostquantitative.

If no catalyst is added the speed of the reaction is largely reduced andonly 40 to 50 per cent of the mixture are reacted within 2 days.

If molecular proportions of chlormethyl methyl ether and1.2-dihydrobenzene are reacted in the presence of some grams of mercuricchloride methoxy-methyl-ch1or-cyclohexene is formed with 65 theevolution of heat. The said product bolls at 81 C. at a pressure of 10millimeters mercury gauge and has the following specific gravity 70Example 5 30 cubic centimeters of liquefied butadiene are shaken for 3days with a solution of 40 grams of benzaldehyde in 80 cubic centimetersof a 25 per 75 cent solution of hydrogen chloride in methanol,

2 grams oi mercuric chloride being added. The formerly colorless layerof the hydrocarbon is substantially increased and colored brown.

Unchanged butadiene is removed. the mixture washed with aqueoussolutions of sodium chorlde and sodium hydroxide and the reactionproduct 1 phenyl l -methoxy-S-chlor-pentene-3, which is identical withthe product descr bed in Example 1 is purified by distillation.

Example 6 20 grams of dihydrobenrene are shaken for three days witha'solution of 50 grams of benzaldehyde in 75 cubic centimeters of a 25per cent solution of hydrogen chloride in methanol 2 grams of mercuricchloride being present. The reaction mixture forming two layers aftershort time is washed with aqueous solutions of sodium chloride andsodium hydroxide. The vmethioxy benzyl-chlor-cyclohexene formed boils at113 to 114 C. at a pressure of 0.1 millimeter mercury gauge. It isidentical with the product described m which R stands for a member ofthe group consisting of hydrogen and alkyl, aralkyl and cry! radicles, Rfor a' member of the group consisting of alkyl, aralkyl and arylradicles and I for halogen with hydrocarbons containing coni lltedolefinic double bonds in the presence of a catalyst.

3. In the production of halogenated ethers the step which comprisesreacting halides of the general formula in which It stands for a memberof the group con-. sisting of hydrogen and alkyl, aralkyl and arylradicles, R for a member of the group consisting of alkyl, aralkyl andaryl radicles and X for halogen with hydrocarbons containing conjugatedolefinic double bonds in the presence of a catalyst and of solvents.

4. In the production of halogenated ethers the.

step which comprises reacting halides of the general formula n on X a xin which It stands for a member of the group consisting of hydrogen andalkyl, aralkvl and aryl radicles, R for a member oi the group consistingof alkyl, aralkyl and aryl radicles and x for halosen with butadiene.

5. The process for the production of haloin which R. stands for a memberof the group congenated ethers which comprises reacting chlorsisting ofhydrogen and. alkyi, aralkyl and aryl methyl methyl ether withbutadiene. radicles. R for a. member of the group consisting 6. Theprocess for the production of haloof alkyl, aralkyl and aryl radiclesand X for halo- 5 genated ethers which comprises reacting alphagen withdihydrobenzene. 5

chlorbenzyl methyl ether with butadiene. 8. The process for theproduction of halo- 7. In the production of halogenated ethers thegenated ethers which comprises reacting chlorstep which comprisesreacting halides oi the genmethyl methyl ether with dihydrobenzene; eralformula 10 OR FRI'I'Z STRAUS- 10

